WO2019077947A1 - Composition d'agent de revêtement fluoré, agent de traitement de surface, et article - Google Patents

Composition d'agent de revêtement fluoré, agent de traitement de surface, et article Download PDF

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Publication number
WO2019077947A1
WO2019077947A1 PCT/JP2018/035582 JP2018035582W WO2019077947A1 WO 2019077947 A1 WO2019077947 A1 WO 2019077947A1 JP 2018035582 W JP2018035582 W JP 2018035582W WO 2019077947 A1 WO2019077947 A1 WO 2019077947A1
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group
fluorine
represented
integer
carbon atoms
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PCT/JP2018/035582
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English (en)
Japanese (ja)
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松田　高至
祐治 山根
隆介 酒匂
理佐 片山
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信越化学工業株式会社
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Priority to JP2019549170A priority Critical patent/JP6888685B2/ja
Priority to KR1020207013996A priority patent/KR20200072515A/ko
Priority to CN201880068293.3A priority patent/CN111315834B/zh
Publication of WO2019077947A1 publication Critical patent/WO2019077947A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a coating agent containing a hydrolyzable alkoxy group or aryloxy group-containing silane modified with a fluoropolyether group-containing polymer and / or a partial hydrolytic condensate thereof, particularly in vacuum deposition coating, Fluorine-containing coating composition capable of improving the curing rate afterward and capable of forming a stable film in a short time, a surface treatment agent containing the coating agent composition, and treatment with the surface treatment agent To provide the
  • the fluoropolyether group-containing compound has water and oil repellency, chemical resistance, lubricity, releasability, antifouling property and the like because its surface free energy is very small.
  • industrially it is widely used in industrial applications such as water- and oil-repellent soiling agents such as paper and fibers, lubricants for magnetic recording media, oil-proofing agents for precision equipment, mold release agents, cosmetics, and protective films.
  • its properties mean that it is at the same time non-adhesive and non-adhesive to other substrates, and although it can be applied to the substrate surface, it is difficult to adhere the film to the substrate Met.
  • silane coupling agents are well known as those for bonding a substrate surface such as glass or cloth to an organic compound, and are widely used as coating agents for various substrate surfaces.
  • the silane coupling agent has an organic functional group and a reactive silyl group (generally, a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule.
  • the hydrolyzable silyl group causes a self condensation reaction due to moisture and the like in the air to form a film.
  • the coating forms a durable and durable coating by chemically and physically bonding the hydrolyzable silyl group to the surface of glass, metal or the like.
  • Patent Documents 1 to 8 Japanese Patent Laid-Open Nos. 2003-238577, 2860979, 4672095, and 2008-534696. Gazette, JP-A-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833).
  • compositions are generally used diluted with a solvent capable of dissolving the fluoropolyether group-containing silane compound.
  • the dilution concentration varies depending on the application method, but is often used in the range of 10 to 50% by mass in the case of vapor deposition coating, and 0.03 to 5% by mass in the case of spray coating, dipping coating, etc. Often used in range.
  • the fluoropolyether group-containing polymer used in these compositions compounds containing an alkoxysilyl group such as a methoxy group or an ethoxy group as a hydrolyzable silyl group are mainly used.
  • deposition coating takes the step of heating and evaporating the polymer component in vacuum to adhere to the substrate, but when the additive is easily volatilized, it evaporates before the polymer and is drawn to the vacuum line side There is a problem that it is easy to be fixed, and it is difficult to fix on the substrate, and a sufficient effect can not be obtained.
  • the present invention has been made in view of the above circumstances, and particularly in vacuum deposition coating, by improving the curing speed after coating, performance expression such as wear durability is accelerated, and a stable film is formed in a short time. It is an object of the present invention to provide a fluorine-containing coating composition that can be used, a surface treatment agent containing the coating agent composition, and an article treated with the surface treatment agent.
  • the present invention provides the following fluorine-containing coating composition, a surface treatment agent containing the coating agent composition, and an article treated with the surface treatment agent.
  • B A silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and / or a partial hydrolytic condensate thereof, wherein the hydrolyzable silyl group is an acyloxysilyl group and / or aroyl A compound which is an oxysilyl group.
  • the silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of the component (A) has the following general formula (1): -C g F 2g O- (1) (Wherein, g is independently an integer of 1 to 6 per unit) Embedded image containing 10 to 200 of the repeating units represented by the following general formula (2a) at the end of the fluoropolyether group-containing polymer: (Wherein, R 1 is an alkyl group having 1 to 4 carbon atoms, an alkoxy substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may be a hydrogen atom partially substituted with a halogen atom) It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is 2 or 3.)
  • the fluorine-containing coating agent composition according to [1] which has at least one hydrolyzable alkoxysilyl group and / or aryloxysilyl group shown by the above
  • the silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (B) is represented by the following general formula (1) -C g F 2g O- (1) (Wherein, g is independently an integer of 1 to 6 per unit) Embedded image containing 10 to 200 of the repeating units represented by and at least one end of the fluoropolyether group-containing polymer represented by the following general formula (2b) (Wherein R 2 is an alkyl group having 1 to 4 carbon atoms, an alkoxy substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may be a hydrogen atom partially substituted with a halogen atom) It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a ′ is 1, 2 or 3.
  • Rf is — (CF 2 ) d —O— (CF 2 O) p (CF 2 CF 2 O) q (CF 2 CF 2 CF 2 O) r (CF 2 CF 2 CF 2 O) s (CF (CF 3) CF 2 O) t - (CF 2)
  • A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group in which the end is —CF 3 group, —CF 2 H group or —CFH 2 group, and Q may be a single bond or fluorine substitution
  • a divalent organic group, Z is a single bond, a diorganosilylene group
  • a is an integer of 1 to 7 and is a group selected from the group having a hydrolyzable silyl group represented by Y is a divalent group having an alkoxysilyl group, aryloxysilyl group, acyloxysilyl group or aroyloxysilyl group, ⁇ is an integer of 1 to 10, and B is a hydrogen atom having 1 to 4 carbon atoms Or a halogen atom.
  • Y is at least one selected from the groups represented by the following general formulas (8) to (10).
  • X is a group represented by the above general formula (2a) or (2b), and D is a single bond or a divalent organic group having 1 to 20 carbon atoms which may be substituted by fluorine.
  • D ′ is a C 1 to C 10 optionally substituted divalent organic group, R 3 is a C 1 to C 20 monovalent hydrocarbon group, and e is 1 or 2.
  • Q is selected from a single bond or a divalent group represented by the following formula.
  • A is a fluorine atom, a hydrogen atom, or a terminal having a —CF 3 group, a —CF 2 H group or a —CFH 2 group.
  • Valent fluorine-containing group [11] A surface treatment agent comprising the fluorine-containing coating composition according to any one of [1] to [10]. [12] The surface treatment agent according to [11], which is further diluted with a solvent containing a fluorine atom. [13] An article treated with the surface treatment agent according to [11] or [12]. [14] The touch panel processed by the surface treating agent as described in [11] or [12]. [15] An antireflective treated article treated with the surface treatment agent according to [11] or [12]. [16] Glass treated with the surface treatment agent according to [11] or [12], tempered glass, sapphire glass, quartz glass or a SiO 2 treated substrate.
  • the fluorine-containing coating agent composition of the present invention comprises a silane containing a hydrolyzable alkoxysilyl group and / or an aryloxysilyl group modified with a fluoropolyether group-containing polymer and / or a partial hydrolysis condensate thereof.
  • the coating composition comprises a hydrolyzable acyloxysilyl group and / or an alayyloxysilyl group having a molecular weight distribution basically equal to that of the above-mentioned polymer and from which an acetic acid compound having catalytic activity is released by hydrolysis.
  • the two types of polymer are simultaneously evaporated, uniformly dispersed and coated on the substrate, and then the catalyst compound is uniformly generated by hydrolysis.
  • the curing speed after coating is improved to form a stable uniform film in a short time.
  • wet curing spray coating and dipping
  • curing is also effective in promoting curing.
  • the fluorine-containing coating agent composition of the present invention is (A) a silane having a hydrolyzable silyl group modified with a polymer containing a fluoropolyether group and / or a partial hydrolytic condensate thereof, which comprises the hydrolyzable silyl.
  • the components (A) and (B) are different from each other in the hydrolyzable silyl group bonded to the silicon atom ((A) component is an alkoxysilyl group and / or an aryloxysilyl group, the component (B) is Is an acyloxysilyl group and / or an aroyloxysilyl group)), and the structure of the other silane modified with the fluoropolyether group-containing polymer has a similar molecular weight distribution The same structure may be used, or different structures may be used.
  • the fluoropolyether group of the component (A) is represented by the following general formula (1) -C g F 2g O- (1) (Wherein, g is independently an integer of 1 to 6 per unit) And 10 to 200, preferably 20 to 100, of the repeating units represented by and at least one end, preferably one or two ends, more preferably one of the fluoropolyether group-containing polymer
  • the following general formula (2a) at the end (Wherein, R 1 is an alkyl group having 1 to 4 carbon atoms, an alkoxy substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may be a hydrogen atom partially substituted with a halogen atom) It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is 2 or 3.) Those having at least one hydrolyzable alkoxysilyl
  • the component (A) has at least one, preferably 1 to 12, hydrolyzable alkoxysilyl group and / or aryloxysilyl group represented by the above formula (2a) in the molecule, and is more preferable. It is desirable that 1 to 6 be included.
  • the fluoropolyether group of the (B) component is represented by the following general formula (1) -C g F 2g O- (1) (Wherein, g is independently an integer of 1 to 6 per unit) And 10 to 200, preferably 20 to 100, of the repeating units represented by and at least one end, preferably one or two ends, more preferably one of the fluoropolyether group-containing polymer
  • the following general formula (2b) at the end (Wherein R 2 is an alkyl group having 1 to 4 carbon atoms, an alkoxy substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R may be a hydrogen atom partially substituted with a halogen atom) It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a ′ is 1, 2 or 3.)
  • the component (B) has at least one, preferably 1 to 12, hydrolyzable acyloxysilyl group and / or aroyloxysilyl group represented by the above formula (2b), and more preferably It is desirable to have 1 to 6 pieces.
  • the fluoropolyether group may be composed of one kind of these repeating units alone or may be a combination of two or more kinds, and each repeating unit may be randomly bonded.
  • R 1 represents an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, having 1 to 4 carbon atoms, and having carbon atoms
  • alkoxy substituted alkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group and the like, or phenyl groups, and among them, methyl group and ethyl group are preferable.
  • R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which a part of hydrogen atoms may be substituted with a halogen atom, and methyl, ethyl, propyl, isopropyl, butyl, butyl, isobutyl, sec And unsubstituted or halogen-substituted alkyl groups such as -butyl, tert-butyl, trifluoroethyl and trichloroethyl, unsubstituted and halogen-substituted aryl groups such as phenyl and the like. Among them, methyl and ethyl are preferable.
  • R 2 represents an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, having 1 to 4 carbon atoms, and having carbon atoms
  • alkoxy substituted alkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group and the like, or phenyl groups, and among them, methyl group and ethyl group are preferable.
  • R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which a part of hydrogen atoms may be substituted with a halogen atom, and methyl, ethyl, propyl, isopropyl, butyl, butyl, isobutyl, sec And unsubstituted or halogen-substituted alkyl groups such as -butyl, tert-butyl, trifluoroethyl and trichloroethyl, unsubstituted and halogen-substituted aryl groups such as phenyl and the like. Among them, methyl and ethyl are preferable.
  • siloxysilyl group and / or aroyloxysilyl group-containing silane fluoropolyether group-containing polymer-modified hydrolyzable silanes represented by the following general formulas (3), (4), (5) and (6) At least one selected is more preferable.
  • Rf is — (CF 2 ) d —O— (CF 2 O) p (CF 2 CF 2 O) q (CF 2 CF 2 CF 2 O) r (CF 2 CF 2 CF 2 O) s (CF (CF 3) CF 2 O) t - (CF 2)
  • A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group in which the end is —CF 3 group, —CF 2 H group or —CFH 2 group, and Q may be a single bond or fluorine substitution
  • a divalent organic group, Z is a single bond, a diorganosilylene group
  • R f is — (CF 2 ) d —O— (CF 2 O) p (CF 2 CF 2 O) q (CF 2 CF 2 CF 2 O) r (CF 2 CF) 2 CF 2 CF 2 O) s (CF (CF 3 ) CF 2 O) t- (CF 2 ) d- .
  • p, q, r, s and t are each independently an integer of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, r is an integer of 0 to 100, s is An integer of 0 to 50, t is an integer of 0 to 100, and p + q + r + s + t is an integer of 10 to 200, preferably an integer of 20 to 100.
  • the units shown in these parentheses are randomly combined You may d is independently an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 1 or 2.
  • Rf Specifically as Rf, the following can be illustrated.
  • d ' is the same as d above, and p', q ', r', s 'and t' are each an integer of 1 or more, and the upper limit thereof is the above p, q, r, s, t And the sum of p ', q', r ', s' and t' is 1 to 200.
  • u is an integer of 1 or more
  • v is an integer of 1 or more
  • u + v 2 It is an integer of-100.
  • Each repeating unit may be randomly combined.
  • A is a fluorine atom, a hydrogen atom or a monovalent fluorine-containing group whose end is a —CF 3 group, a —CF 2 H group or a —CFH 2 group, and is monovalent Specifically, the following can be illustrated as a fluorine-containing group of these. -CF 3 -CF 2 CF 3 -CF 2 CF 2 CF 3 -CF 2 H -CFH 2
  • Q is a single bond or a divalent organic group which may be substituted with fluorine, and is a linking group between the Rf group and the terminal group.
  • a diorganosilylene group such as an amide bond, an ether bond, an ester bond or a dimethylsilylene group, -Si [OH] [(CH 2 ) b Si (CH 3 ) 3 ]-(b is 2 to 4
  • An unsubstituted or substituted divalent organic group having 2 to 12 carbon atoms which may contain one or more types of structures selected from the group consisting of a group represented by It is an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms which may be contained.
  • examples of the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms include ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), and hexa It may be an alkylene group such as a methylene group or an octamethylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (such as an alkylene arylene group); A part or all of which is substituted with a halogen atom such as fluorine or iodine, and the like are mentioned, and among them, an unsubstituted or substituted alkyl group having 2 to 4 carbon atoms and a phenyl group are preferable.
  • Examples of such Q include the following groups.
  • Z is a single bond, preferably a diorganosilylene group such as a dialkylsilylene group having 1 to 3 carbon atoms
  • -JC [J is preferably an alkyl having 1 to 3 carbon atoms
  • trivalent group represented by -LSi (wherein L is preferably an alkyl group having 1 to 3 carbon atoms), tetravalent group represented by -C-, -Si ⁇ And a group selected from a divalent to octavalent, preferably a divalent to tetravalent siloxane residue, and containing a siloxane bond, the number of silicon atom
  • n is an integer of 2 to 6
  • the organopolysiloxane residue preferably has an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl, or a phenyl group.
  • the alkylene group in the silalkylene bond preferably has 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms.
  • W is a group selected from groups having a hydrolyzable silyl group represented by the following general formulas (7a) to (7d).
  • X is the same as above, f is an integer of 1 to 10, preferably 2 to 8, and D is a single bond or a C 1 to C 20 optionally substituted divalent organic group
  • m is an integer of 2 to 6, preferably 2 to 4, and Me is a methyl group.
  • D is a single bond, or a divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, which may be substituted with fluorine, preferably a divalent hydrocarbon group, and as the divalent hydrocarbon group,
  • Arylene group such as methylene group, ethylene group, propylene group (trimethylene group, methyl ethylene group), butylene group (tetramethylene group, methyl propylene group), hexamethylene group, alkylene group such as octamethylene group, phenylene group, or Examples thereof include combinations of two or more of these groups (such as alkylene and arylene groups) and those in which part or all of the hydrogen atoms of these groups are substituted with fluorine atoms.
  • an ethylene group, a propylene group and a phenylene group are preferable.
  • ⁇ is an integer of 1 to 7, preferably an integer of 1 to 3.
  • Y is a divalent group having a hydrolyzable silyl group selected from alkoxysilyl group, aryloxysilyl group, acyloxysilyl group and aroyloxysilyl group, preferably Is a group represented by the following general formula (8), (9) or (10).
  • D ′ is a divalent organic group having 1 to 10 carbon atoms which may be substituted with fluorine
  • R 3 is a monovalent carbon having 1 to 20 carbon atoms.
  • e is 1 or 2.
  • D ' is a C1-C10, preferably C2-C8, optionally substituted divalent organic group, preferably a divalent hydrocarbon group, and as the divalent hydrocarbon group, a methylene group ,
  • An alkylene group such as ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, arylene group such as phenylene group, or these groups And combinations of two or more thereof (such as alkylene and arylene groups) and those in which part or all of the hydrogen atoms of these groups are substituted with a fluorine atom.
  • an ethylene group and a propylene group are preferable.
  • R 3 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group.
  • Alkyl group such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and octyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group and propenyl group, phenyl group, Examples include aryl groups such as tolyl group, and aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group. Of these, methyl is preferred.
  • Y include the following groups.
  • ⁇ is an integer of 1 to 10, preferably an integer of 1 to 4.
  • B is a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group or a butyl group, a fluorine atom, a chlorine atom or a bromine atom, It is a halogen atom such as iodine atom.
  • fluoropolyether group-containing polymer modified hydrolyzable silane represented by the above formulas (3) and (4) a linking group Q is used. And Z group And a W group containing a hydrolyzable silyl group What is represented as is illustrated below.
  • the combination of Q, Z and W is not limited to these, and by simply changing Q, Z and W, several fluoropolyether group-containing polymer modified hydrolyzable silanes can be obtained.
  • the effect of the present invention can be exhibited with any fluoropolyether group-containing polymer modified hydrolyzable silane.
  • Rfa -CF 2 O- (C 2 F 4 O) q1 (CF 2 O) p1 -CF 2 - and is, p1, q1 is .f1 p ', q' is the same as defined 1 It is an integer of ⁇ 10.
  • Rfb is -CF 2 O- (C 2 F 4 O) q1 (CF 2 O) p1 -CF 2 - and is, p1, q1 .
  • R 4 is the same as p ', q' respectively -CH 2 CH 2 -and / or -CH (CH 3 )-)
  • Rfb is -CF 2 O- (C 2 F 4 O) q1 (CF 2 O) p1 -CF 2 - and is, p1, q1 is the same as p ', q', respectively.
  • the terminal hydrolyzable group of the silane having a hydrolyzable silyl group modified with the above fluoropolyether group-containing polymer may contain partial hydrolytic condensates obtained by partially hydrolyzing and condensing previously by known methods.
  • the molecular weights of the (A) component and the (B) component are the same (for example, the weight average molecular weight of the (B) component is 0.6 to 1.3 times the weight average molecular weight of the (A) component, particularly 0.7 And the weight average molecular weight of each of them is preferably 1,000 to 20,000, 2, More preferably, it is from 1,000 to 10,000. If the weight average molecular weight is too small, the water and oil repellency and low dynamic friction of the fluoropolyether group may not be exhibited. If the weight average molecular weight is too large, adhesion to the substrate may be deteriorated.
  • the weight average molecular weight can be measured as a standard polystyrene equivalent value of gel permeation chromatography (GPC) using AK-225 (manufactured by Asahi Glass Co., Ltd.) as a developing solvent (the same applies hereinafter).
  • GPC gel permeation chromatography
  • the fluorine-containing coating agent composition of the present invention may further contain, as component (C), the following general formula (11) (Wherein, A is as defined above, and Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue) And a fluoropolyether group-containing polymer (hereinafter sometimes referred to as a nonfunctional polymer) represented by
  • A can exemplify the same as A exemplified above, and as A, -F -CF 3 -CF 2 CF 3 -CF 2 CF 2 CF 3 Is preferred.
  • Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue, and may be the same as or different from Rf exemplified above, and as Rf ′, those shown below are preferable.
  • p2 is an integer of 5 to 200, preferably 10 to 100
  • q2 is an integer of 5 to 200, preferably 10 to 100
  • r2 is an integer of 10 to 200, preferably 20 to 100
  • t2 is 5 to 200, preferably an integer of 10 to 100
  • t3 is an integer of 10 to 200, preferably 20 to 100
  • t2 + p2 is an integer of 10 to 200, preferably 20 to 100
  • q2 + p2 is 10 to 200, preferably 20 to 100
  • nonfunctional polymer represented by the formula (11) examples include the following. (Wherein, p2, q2, r2, t2, t3 are the same as above).
  • the weight average molecular weight of the fluoropolyether group-containing polymer of the component (C) is preferably 1,000 to 50,000, more preferably 1,000 to 10,000, and further, the component (A)
  • the weight average molecular weight is preferably in the range of 0.5 to 1.5 times the weight average molecular weight. When the weight average molecular weight is too small, the excellent slipperiness of the component (A) may be impaired, and when it is too large, the transparency of the coating film may be reduced.
  • non-functional polymer of (C) component can use a commercial item and is marketed with the brand name of FOMBLIN, DEMNUM, KRYTOX, for example, it can obtain it easily.
  • FOMBLIN FOMBLIN
  • DEMNUM DEMNUM
  • KRYTOX KRYTOX
  • FOMBLIN Y (trade name of Solvay Solexis, FOMBLIN Y 25 (weight average molecular weight: 3,200), FOMBLIN Y 45 (weight average molecular weight: 4, 100)) (In the formula, t2 'and p2' are numbers satisfying the above weight average molecular weight.)
  • FOMBLIN Z (trade name of Solvay Solexis, FOMBLIN Z 03 (weight average molecular weight: 4,000), FOMBLIN Z 15 (weight average molecular weight: 8,000), FOMBLIN Z 25 (weight average molecular weight: 9, 500)) (In the formula, q2 'and p2' are numbers satisfying the above weight average molecular weight.)
  • DEMNUM (trade name of Daikin Industries, DEMNUM S20 (weight average molecular weight: 2,700), DEMNUM S 65 (weight average molecular weight: 4,500), DEMNUM S 100 (weight average molecular weight: 5,600)) (Wherein, r2 'is a number satisfying the weight average molecular weight.)
  • KRYTOX (trade name of DuPont, KRYTOX 143 AB (weight average molecular weight: 3,500), KRYTOX 143 AX (weight average molecular weight: 4,700), KRYTOX 143 AC (weight average molecular weight: 5, 500), KRYTOX 143 AD (weight average molecular weight) : 7,000)) (In the formula, t3 'is a number satisfying the weight average molecular weight.)
  • the amount of component (C) used is not particularly limited, but it is preferably in the range of 0 to 50% by mass, more preferably 5 to 50% by mass, based on the mass of component (A).
  • hydrolytic condensation catalysts such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate etc.), organic titanium compounds (tetra n-butyl titanate etc.), organic acids (fluorinated carboxylic acids, acetic acid, methane etc. Basic organic compounds such as sulfonic acids etc.), inorganic acids (hydrochloric acid, sulfuric acid etc.), compounds having primary amino group, compounds having secondary amino group, compounds having tertiary amino group, compounds having guanidyl group, etc.
  • hydrolytic condensation catalysts such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate etc.), organic titanium compounds (tetra n-butyl titanate etc.), organic acids (fluorinated carboxylic acids, acetic acid, methane etc. Basic organic compounds such as sulfonic acids etc.), inorganic acids (hydrochloric acid, sulfuric
  • Examples thereof include compounds containing an alkali metal such as lithium, sodium and potassium, and compounds containing an alkaline earth metal such as magnesium and calcium.
  • fluorine-based carboxylic acids, acetic acid, tetra n-butyl titanate, and dibutyltin dilaurate are particularly desirable.
  • the addition amount of the hydrolytic condensation catalyst is a catalytic amount, but is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass with respect to 100 parts by mass of the component (A).
  • the fluorine-containing coating composition of the present invention can be prepared by uniformly mixing the above-mentioned components according to a conventional method.
  • the surface treatment agent of the present invention comprises the above-mentioned fluorine-containing coating composition.
  • the surface treatment agent of the present invention comprising the fluorine-containing coating composition containing the components (A) and (B) is generally a solvent in which these polymers (the components (A) and (B)) can be dissolved. Dissolved and diluted in The dilution solvent is not particularly limited as long as it can be uniformly dissolved.
  • fluorine-modified aliphatic hydrocarbon solvents perfluorohexane, perfluoroheptane, perfluorooctane and the like
  • fluorine-modified aromatic hydrocarbon solvents m-xylene hexafluoride, benzotrifluoride, 1,3-trifluoromethylbenzene etc.
  • fluorine modified ether solvents methyl perfluoropropyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran) etc
  • fluorine modified alkylamine solvents Perfluorotributylamine, perfluorotripentylamine, etc.
  • partially fluorinated modified solvent (1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,1,2,2 , 3, 4, 5, 5, 5-decaful Ropentane, 1,1,1,2,2,3,3,4,
  • fluorine-modified fluorinated solvents are preferable in terms of solubility, wettability and the like, and in particular, ethyl perfluorobutyl ether, decafluoropentane and 1,1,1,3,3-pentafluorobutane are preferable. More preferable.
  • the above solvents may be used alone or in combination of two or more.
  • the optimum concentration of the components (A) and (B) to be dissolved in the solvent varies depending on the method of coating treatment, but the content of the component (A) in the entire surface treatment agent comprising the fluorine-containing coating composition and the solvent
  • the amount is preferably in the range of 0.01 to 50% by mass, and more preferably in the range of 0.03 to 25% by mass.
  • concentration of the component (A) is too low, sufficient antifouling property and water / oil repellency can not be obtained after the coating treatment, and when too high, the coating film becomes nonuniform, the transparency decreases, and the surface becomes sticky.
  • the surface treatment agent comprising the fluorine-containing coating composition of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying and vapor deposition.
  • the curing temperature varies depending on the curing method. For example, when applied by spray method, ink jet method, dipping method, brush coating, vacuum evaporation method, room temperature (20 ° C.) to 200 ° C., particularly 50 to 150 ° C. The range of is desirable.
  • As curing humidity it is desirable to carry out under humidification in order to accelerate the reaction.
  • the thickness of the cured film is appropriately selected depending on the type of the substrate, but is usually 0.1 to 100 nm, and particularly 3 to 30 nm. If the adhesion is poor, the adhesion can be improved by providing a SiO 2 layer as a primer layer, or performing vacuum plasma treatment, atmospheric pressure plasma treatment, or alkali treatment.
  • the substrate to be treated with the surface treatment agent comprising the fluorine-containing coating composition of the present invention is not particularly limited, and various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, quartz, etc. It may be.
  • the surface treatment agent comprising the fluorine-containing coating composition of the present invention can impart water and oil repellency, chemical resistance, releasability, low dynamic friction, and stain resistance to these substrates. In particular, excellent anti-soiling performance can be imparted without impairing the transparency and texture of various articles, and the base material can be protected from the intrusion of chemicals and the like, and the anti-staining performance can be maintained for a long time.
  • the articles to be treated with the surface treatment agent comprising the fluorine-containing coating composition of the present invention include optical articles, films, glass, quartz substrates, antireflective films and the like, and in particular touch panels, reflections It is used for prevention treatment articles, glass, tempered glass, sapphire glass, quartz glass, and SiO 2 treated substrates.
  • the following compounds A1 to A4 are modified with a fluoropolyether group-containing polymer as a hydrolyzable alkoxysilyl group modified with a fluoropolyether group-containing polymer and / or an aryloxysilyl group-containing silane (A)
  • the following compounds B1 and B2 were prepared as the functional acyloxysilyl group and / or aroyloxysilyl group-containing silane (B).
  • Compound A1 (Weight average molecular weight: 4,600)
  • C1 and C2 were prepared as curing catalysts for comparative examples.
  • C1 trifluoroacetic acid
  • C2 acetic acid
  • Example 1 to 6 Preparation of Surface Treatment Agent
  • any of the components A1 to A4 described above and any of the components B1 and B2 were mixed with the compositions described in Table 1 below (mixtures 1 to 6)
  • the surface treatment agent was prepared by dissolving in 400 parts by weight of Novec 7200 (manufactured by 3M) so that the concentration of the mixture (total 100 parts by weight) would be 20% by mass.
  • any of the components A1 to A4 described above, or this, and any of the curing catalysts C1 and C2 for Comparative Example are mixed in the composition described in Table 2 below (mixtures 7 to 12)
  • the surface treatment agent was prepared by dissolving in 400 parts by weight of Novec 7200 (manufactured by 3M) such that the concentration of the mixture (total 100 parts by weight) was 20% by mass.
  • the cured film in the above-mentioned test body was evaluated by the following method.
  • [Water repellency] The contact angle of the cured film to water was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). The results are listed in Table 3 below.
  • Comparative Examples 1 to 6 of Examples 1 to 6 and Comparative Examples 1 to 4 are polymers having an acyloxysilyl group at the end having the same molecular weight distribution in the polymer (A) having an alkoxysilyl group at the end It is a case where B) is added and blended.
  • Comparative Examples 1 to 4 are cases where only the polymer (A) is used and the polymer (B) is not blended.
  • the curing is accelerated by the acid (acetic acid) generated by the hydrolysis of the polymer (B).
  • Comparative Examples 1 to 4 are only polymers of terminal alkoxysilane (methoxysilane), so hydrolysis is slow, film curing on the substrate is slow, and abrasion durability is inferior to those of Examples.
  • Comparative Examples 5 and 6 of Example 6 and Comparative Examples 5 and 6 are examples in which an organic acidic compound is added as a catalyst in place of the component (B).
  • these additives have a low boiling point, they are easily attracted to the vacuum exhaust line side and can hardly be fixed on the substrate surface, so no curing acceleration effect is seen and nothing is added It was at the same level as Comparative Example 4.

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  • Wood Science & Technology (AREA)
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Abstract

Selon l'invention, il est possible d'obtenir une composition d'agent de revêtement fluoré qui contient (A) un silane possédant un groupe aryloxy silyle et/ou un groupe alcoxy silyle modifié par un polymère comprenant un groupe fluoropolyéther, et ou un condensat d'hydrolyse partielle de ce silane, et (B) un silane possédant un groupe aroyloxy silyle et/ou un groupe acyloxy silyle modifié par un polymère comprenant un groupe fluoropolyéther, et ou un condensat d'hydrolyse partielle de ce silane, le rapport massique des ces silanes étant compris dans une plage telle que （Ａ）／（Ｂ）＝９９,９／０,１～８０／２０ (pour un total de 100), ainsi il est possible d'améliorer la vitesse de durcissement après application, particulièrement lors d'un revêtement par dépôt sous vide, et de former un revêtement uniforme et stable sur une courte durée.
PCT/JP2018/035582 2017-10-20 2018-09-26 Composition d'agent de revêtement fluoré, agent de traitement de surface, et article WO2019077947A1 (fr)

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WO2023132276A1 (fr) * 2022-01-05 2023-07-13 Ａｇｃ株式会社 Composition, procédé de production de composition, liquide de revêtement, article et procédé de production d'article
WO2023136144A1 (fr) * 2022-01-11 2023-07-20 Ａｇｃ株式会社 Agent de traitement de surface, article, procédé de fabrication d'article
WO2023136143A1 (fr) * 2022-01-11 2023-07-20 Ａｇｃ株式会社 Agent de traitement de surface, article et procédé de production d'article
WO2023149340A1 (fr) * 2022-02-04 2023-08-10 Ａｇｃ株式会社 Agent de traitement de surface, article et procédé de production d'article
WO2023149339A1 (fr) * 2022-02-04 2023-08-10 Ａｇｃ株式会社 Agent de traitement de surface, article et procédé de production d'article

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JP7446215B2 (ja) * 2020-12-17 2024-03-08 信越化学工業株式会社 硬化型コーティング組成物、及び物品

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WO2023136144A1 (fr) * 2022-01-11 2023-07-20 Ａｇｃ株式会社 Agent de traitement de surface, article, procédé de fabrication d'article
WO2023136143A1 (fr) * 2022-01-11 2023-07-20 Ａｇｃ株式会社 Agent de traitement de surface, article et procédé de production d'article
WO2023149340A1 (fr) * 2022-02-04 2023-08-10 Ａｇｃ株式会社 Agent de traitement de surface, article et procédé de production d'article
WO2023149339A1 (fr) * 2022-02-04 2023-08-10 Ａｇｃ株式会社 Agent de traitement de surface, article et procédé de production d'article

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